frasch



STATES PATENT mun,

HANS A. FRASCH, OF CLEVELAND, OHIO, ASSIGNOR TO THE GRASSELLI CHEMICALCOMPANY, OF SAME PLACE.

BROWN PETROL EUIVI NITRO DYE.

SPECIFICATION forming part of Letters Patent No. 518,991, dated May 1,1894.

Application filed April 19, 1893. Serial No. 471,018. (Specimens-l ToaZZ whom it may concez n-f Be it known that I, HANsA. FRASCH, a citizenof the United States, residing at Cleveland, in the county of Cuyahogaand State of Ohio, have invented certain new and useful Improvements inMethods of Obtaining Dye- Stuffs from Hydrocarbons by Nitration; and Ido hereby declarethat the following is a full, clear, and exactdescription of the invention, which will enable others skilled in theart to which it appertains to make and use the same.

In the manufacture of anilin, artificial alizariu, and kindred dyestuffsand bases for dye stuffs and colors, coal'tar obtained from illuminatinggas works has hitherto been employed; The ordinary process of conversionis by fractional distillation of the coal tar. The aromatic series ofhydrocarbons contamed in such coal tar furnishes the source whence thesedyestuffs or colors have been derived. Akindred or similar series ofhydrocarbons exists also in petroleum or natural mineral oil or thedistillates or derivatives, residual or otherwise, thereof; and it isupon these hydrocarbons of the petroleum series as distinguished fromthe hydrocarbons of the coal tar series that I act for obtaining my newdyestuffs.

My invention relates, first, to a method of obtaining dyestuffs fromhydrocarbons contained in such natural oils by nitration, and second, tothe product so obtained.

In practicing my invention, I subject crude petroleum or its distillatesor products, residual or otherwise, to the action of a mixture ofsulfuric and nitric acids until all the arcmatic hydrocarbons, olefines,naphthenes and unsaturated hydrocarbons in the oil are taken up in theacid mixture as oxidized and corresponding nitro products. I prefer touse one part of nitric acid to three parts of sulfuric acid in themixture, but these proportions may be varied; and so also the proportionof acid mixture to oil may be varied, according to the quality of theoil being treated, and according to the quantity of sulfuric and otheracids-that may be in the petroleum or its products being treated. Crudeoil requires about twenty-five per cent, while distillates require fromtwo to ten per cent, and sludge from nothing to five per cent, accordingto the quantity of acid remaining in the substance. In all cases, thetreatment proceeds alike, substantially as follows: The mixture of acidand oil is agitated, mechanically or by a forced current of air, atordinary temperatu res say, 15 to 20 Celsius, until a sample from whichthe acid has been permitted to settle will discolor little, if any, uponthe addition thereto of fresh concentrated acid. The mixture of acid andoil isthen permitted to rest until the acid is separated from the oil,when the acid containing the aromatic hydrocarbons and tarry substancesis drawn from the oil. The acid mixture taken from the oil is thenheated to from to Celsius, until the hydrocarbons contained therein areconverted into nitro or oxidized products. Nitration maybe effectedwithout heat by keeping the mixture agitated a long time, say, from fourto eight weeks, and even longer, thus permitting the acid to act uponthe hydrocarbous. The requisite degree or extent of nitration isdetermined when the bulk of a test sample will dissolve in a hotsolution of alkali. The free acid is then removed and this may bereadily accomplished by neutralization or repeatedly washing the mixturewith cold water or by precipitating the nitro com pound from the acid.After the free acid is removed, the residuum is heatedwith water untilthe water is saturated with the more soluble nitro products. Thesolution is left to'settle, when the soluble products and the insolublematter and oily matter are separated by decantation. The solubleproducts are then drawn off and consist in a mixture of different higheror lower nitro products. To separate these products carbonate of lime orcaustic soda. is added, with or without heating, until precipitationceases, whereby a soluble and an insoluble calcium salt are obtained.Any other substance such as barium or lead, which will form a solubleand an insoluble salt with the nitro product may or any other saltinwhose Watery solution the dyestuff is insoluble. The dyestuif is thenseparated by filtration.

Instead of obtaining the dyestuff directly, as just described, it may beobtained indirectly by converting the calcium salt into a salt ofpotassium, ammonium, &c., and then separating the dyestuif as before.

The insoluble salt separated from the solution first above mentioned maybe converted into a soluble salt by the addition thereto of carbonate ofsodium, potassium, ammonium,

or any other substance that will unite there with and form a solublecompound or dyestuff and displace the calcium. The dyestuff itself isprecipitated from the solution thereby obtained by the addition ofhydrochloric acid, sodium chlorid, or any other salt in whose solutionthe dyestutf is insoluble.

The treatment of this insoluble salt and the dyestuif obtained therefromform the subject-matter of an application filed by me as a divisionhereof, Serial No. 489,0l2, filed October 24, 1893.

The dyestuif obtained by the method first above described is in the formof a reddish brown powder, soluble in water and glycerin and acetone. Inits solutions, and more especially its acetone solutions, it has abluish green fluorescence. It forms a soluble calcium salt and emits thecharacteristic odor of burning coal oil when exposed to high heat. Itdyes silk and wool, in acidulated solutions, without mordant, a reddishbrown.

The dyestulf obtained by the second mentioned process is a distinctbrown color and in the form of a powder. It has a resinous appearance ortexture when first made, but can be pulverized. This dyestuff is solubleslightly in cold water, but readily soluble in hot water. It is alsosoluble in acetone and glycerin. It forms an insoluble calcium salt, andis thus mainly distinguished from the first named salt. It emits thecharacteristic odor of burning coal oil when highly heated, and dylescotton, without mordant, a brownish co or.

If instead of using a mixture of sulfuric acid and nitric acid, sulfuricacid be substituted in the process above described,a sulfo product willbe obtained. In contemporaneous applications (Serial Nos. 471,016 and471,017, filed April 19, 1893) I have fully described this sulfo processand product, and to them reference is hereby made for furtherparticulars. The sulfo product referred to may be treated to obtain anitro product by dissolving the finished sulfo product in water andheating it with nitric acid until eifervescence ceases, after which theproduct is precipitated from the solution as before. The same or asimilar body may be obtained by the addition to awatery solution of thesulfo product of sodium nitrite and hydrochloric acid, and it can beobtained also by the ad dition of nitrous acid to the sulfo product.

What I claim is 1. The art of manufacturing dyestulfs by nitration ofpetroleum, natural mineral oils, or the residuum of the distillation orrefining thereof, with nitro-sulfuric acid, washing the resultingproducts with water, then heating with water, allowing the insolublematter to settle, and removing the solution from the sediment andtreating it with a base, such as lime, and thereby forming a soluble andan insoluble salt, and precipitating from the soluble salt solution thedyestuff by the addition of a reagent, such as sodium chlorid,substantially as, described.

2. As an article of manufacture, a petroleum product which is a nitrobody in the form of a reddish brown powder, soluble in water, glycerin,and acetone, and which is capable of dyeing wool or silk, withoutmordant, a reddish brown color, and whose calcium salt is soluble inwater, substantially as described.

\Vitness my hand to the foregoing specification.

HANS A. FRASOI-I.

Witnesses:

H. T. FISHER, GEORGIA SCHAEFFER.

